Cationic acetylacetonate palladium complexes/boron trifluoride etherate catalyst systems for polymerization of 5-methoxycarbonylnorbornene

A simple protocol using cationic acetylacetonate palladium complexes with mono-/bidentate phosphine ligands activated with BF 3 ·OEt 2 as in situ -formed catalyst for polymerization of endo/exo mixture of 5-methoxycarbonylnorbornene (activity up to 1.1·10 4  g mol − 1  h − 1 ) or 5-phenylnorbornene (7.2·10 5  g mol − 1  h − 1 ), and norbornene (3.3·10 8  g mol − 1  h − 1 ) have been developed. It was observed that the ligands nature strongly influence the catalytic activity. The catalyst system Pd(II)/BF 3 ·OEt 2 was also active for the copolymerization of norbornene with 5-methoxycarbonylnorbornene. DFT calculations of isomers upon single insertion of 5-methoxycarbonylnorbornene into Pd H bond and NMR/FTIR studies for pre-catalyst activation mechanism were performed.